化学镀法制备钼铜复合材料的研究
摘要
本文采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、俄歇电子分析(AES)和X射线光电子分析(XPS)等分析手段研究了钼粉表面化学镀铜方法及钼铜复合粉的烧结工艺。深入探讨了化学镀铜液组成及施镀工艺条件对钼粉表面化学镀铜的影响,并对钼粉表面化学镀铜的反应机理及铜在钼粉表面的生长情况进行了研究。此外,对银催化化学镀法制备钼铜复合粉体的改良工艺及银催化钼粉表面化学镀铜的工艺机理进行了研究。最后初步探讨了钼铜复合粉的烧结工艺。论文得出如下结论:
(1)化学镀铜前的预处理可以使钼粉具有较好的分散性和催化活性。合理的化学镀液组成和施镀工艺可以获得铜含量为15%～85%(wt.%)的钼铜复合粉体,反应速度快,粉末分散,铜镀层均匀,但表面粗糙。钼粉表面化学镀铜工艺为:TEA和EDTA为络合剂,聚乙二醇和2,2'-联吡啶为双稳定剂,pH值:12～13,温度:50～55℃,甲醛:24～28ml/L,硫酸铜:15g/L与络合剂含量摩尔比为1:5,超声波和磁力搅拌。
(2)得出了钼粉表面化学镀铜的反应机理。预处理过程中,利用SnCl_2(敏化剂)将PdCl_2(活化剂)还原成Pd~0原子簇沉积在钼粉表面,pd~0原子簇将作为化学镀铜的催化核心,使反应继续进行。化学镀铜过程中小的Pd原子簇尺寸造成Pd结合能的正偏移并估算出了Pd原子簇的尺寸为3～4nm;结合化学镀铜反应机理和化学镀铜过程不同阶段钼粉表面的形貌分析,提出了铜在钼粉表生长的“扩散—缩小自催化沉积”模型。
(3)Ag原子簇可以作为化学镀铜过程的催化核心,成功地制备出铜包钼的钼铜复合粉体;探讨了银催化钼粉表面化学镀铜的工艺机理,H_2PO_2~-将敏化处理后粘附在钼粉表面的银氨还原成Ag原子簇沉积在钼粉表面,Ag原子簇作为化学镀铜的催化核心,使铜沉积在钼粉表面。
(4)钼铜复合粉末经过350℃/60min的氢气还原处理可以有效提高烧结体的最终致密度;用化学镀方法制备的钼铜复合粉体成形性好,生坯相对密度可以达到87%,但是成形压力较大,达到1600MPa。
(5)探讨了钼铜复合粉压坯的液相烧结和固相烧结方法。液相烧结(1200℃/2h)制备出的烧结体表面有铜渗出、坍塌等现象,不是制备钼铜复合材料的理想方法。对固相烧结制备出的烧结体进行了致密度、电导率、热导率、热膨胀系数和硬度的检测。结果表明,由于化学镀铜法制备的钼铜复合粉特殊的结构,使钼铜复合粉压坯在低于铜熔点温度下进行固相烧结,即能得到良好的性能。
In the investigation, the method of copper coating on the surface of the molybdenum powders with the electroless plating and technique of Mo/Cu composite powders sintering were studied with the aid of X-ray diffraction (XRD), scanning electron microcopy (SEM), transmission electron microcopy (TEM), auger electron spectrometer (AES) and X-ray photoelectron spectrometer (XPS). The influence of solution composition and plating conditions on electroless copper plating was studied. The reaction mechanism of electroless copper coating of molybdenum powders and the growth mechanism of copper growth on the surface of the molybdenum powders were suggested. Besides, the electroless deposition of copper on the surface of molybdenum powders by using silver as catalyst was investigated and the possible mechanism of electroless copper coating of molybdenum by using silver as catalyst was proposed. Finally, the technique of Mo/Cu composite powders sintering was researched primarily. The results are as follows:
(1) Through pretreatment before electroless copper plating, the Molybdenum powders had better dispersity and catalytic activity. Through rational solution composition and plating conditions, Mo/Cu composite powders with a range content of copper from 15～85wt.% can be successfully obtained. The coating rate was fast and the composite powders with continuous lay of copper but rough surface were dispersive. The plating technique was that TEA and EDTA as complex agents, the 2, 2'-bipyridyl and PEG as double stabilizers, pH value 12～13, temperature 50～55℃, formaldehyde 24～28ml/L, metal salt 15g/L, whose mole ratio to the complex agent content was 1:5, ultrasonic and magntic stiring.
(2) The reaction mechanism of electroless copper coating was mainly studied with the help of XPS, which shows the reduction PdCl_2 (activator) catalyst on the surface of molybdenum powders by SnCl_2 (sensitizer) to produce pure Pd~0 clusters, which subsequently act as nucleation sites for copper depositon. The concept of XPS core-level binding energy(BE) shift due to small cluster size was utilized to predict the size of pure Pd~0 clusters deposited on the surface of molybdenum powders, which were about 3～4 nm. Combination the reaction mechanism of electroless copper coating and the morphologies of the copper coated powders at the different stages in this experiment, the diffusion-shrinkage autocatalytic model was supposed for the growth mechanism over the surface.
(3) The metallic Ag~0 clusters acted as nucleation sites for the copper deposition and the copper coated molybdenum composite powders can be acquired successfully. With the analysis of XPS, the reaction mechanism of electroless copper coating of molybdenum powders as Ag catalysis was suggested. After the sensitization step, the reducing agent(H_2PO_2~-) in the bath immediately reduced the [Ag(NH_3)_2]~+ ions adsorbed on the molybdenum to the metallic Ag~0 clusters which subsequently act as nucleation sites for copper depositon.
(4) The Mo/Cu composite powders were reducing treated for 60min at 350℃, which can improve the final densification of the compact. The Mo/Cu composite powders had good formability. The green compact of the relative density can reached up to 87%, however it needed higher forming pressure.
(5) The preparation of Mo/Cu composite materials with liquid sintering and solid sintering methods was discussed, respectively. The liquid sintering method was not ideal way to fabricate the Mo/Cu composite materials, because after liquid sintering the phenomena of copper exudation and collapse were observed. After Mo/Cu green compacts were sintered to composite materials at temperature that was lower than the melting point of copper. The conductivity, heat conductivity, heat expansion coefficient and rigid were detected. The results showed that properties composites materials were excellent due to the special structure of Mo/Cu composite powders.
(1)化学镀铜前的预处理可以使钼粉具有较好的分散性和催化活性。合理的化学镀液组成和施镀工艺可以获得铜含量为15%～85%(wt.%)的钼铜复合粉体,反应速度快,粉末分散,铜镀层均匀,但表面粗糙。钼粉表面化学镀铜工艺为:TEA和EDTA为络合剂,聚乙二醇和2,2'-联吡啶为双稳定剂,pH值:12～13,温度:50～55℃,甲醛:24～28ml/L,硫酸铜:15g/L与络合剂含量摩尔比为1:5,超声波和磁力搅拌。
(2)得出了钼粉表面化学镀铜的反应机理。预处理过程中,利用SnCl_2(敏化剂)将PdCl_2(活化剂)还原成Pd~0原子簇沉积在钼粉表面,pd~0原子簇将作为化学镀铜的催化核心,使反应继续进行。化学镀铜过程中小的Pd原子簇尺寸造成Pd结合能的正偏移并估算出了Pd原子簇的尺寸为3～4nm;结合化学镀铜反应机理和化学镀铜过程不同阶段钼粉表面的形貌分析,提出了铜在钼粉表生长的“扩散—缩小自催化沉积”模型。
(3)Ag原子簇可以作为化学镀铜过程的催化核心,成功地制备出铜包钼的钼铜复合粉体;探讨了银催化钼粉表面化学镀铜的工艺机理,H_2PO_2~-将敏化处理后粘附在钼粉表面的银氨还原成Ag原子簇沉积在钼粉表面,Ag原子簇作为化学镀铜的催化核心,使铜沉积在钼粉表面。
(4)钼铜复合粉末经过350℃/60min的氢气还原处理可以有效提高烧结体的最终致密度;用化学镀方法制备的钼铜复合粉体成形性好,生坯相对密度可以达到87%,但是成形压力较大,达到1600MPa。
(5)探讨了钼铜复合粉压坯的液相烧结和固相烧结方法。液相烧结(1200℃/2h)制备出的烧结体表面有铜渗出、坍塌等现象,不是制备钼铜复合材料的理想方法。对固相烧结制备出的烧结体进行了致密度、电导率、热导率、热膨胀系数和硬度的检测。结果表明,由于化学镀铜法制备的钼铜复合粉特殊的结构,使钼铜复合粉压坯在低于铜熔点温度下进行固相烧结,即能得到良好的性能。
In the investigation, the method of copper coating on the surface of the molybdenum powders with the electroless plating and technique of Mo/Cu composite powders sintering were studied with the aid of X-ray diffraction (XRD), scanning electron microcopy (SEM), transmission electron microcopy (TEM), auger electron spectrometer (AES) and X-ray photoelectron spectrometer (XPS). The influence of solution composition and plating conditions on electroless copper plating was studied. The reaction mechanism of electroless copper coating of molybdenum powders and the growth mechanism of copper growth on the surface of the molybdenum powders were suggested. Besides, the electroless deposition of copper on the surface of molybdenum powders by using silver as catalyst was investigated and the possible mechanism of electroless copper coating of molybdenum by using silver as catalyst was proposed. Finally, the technique of Mo/Cu composite powders sintering was researched primarily. The results are as follows:
(1) Through pretreatment before electroless copper plating, the Molybdenum powders had better dispersity and catalytic activity. Through rational solution composition and plating conditions, Mo/Cu composite powders with a range content of copper from 15～85wt.% can be successfully obtained. The coating rate was fast and the composite powders with continuous lay of copper but rough surface were dispersive. The plating technique was that TEA and EDTA as complex agents, the 2, 2'-bipyridyl and PEG as double stabilizers, pH value 12～13, temperature 50～55℃, formaldehyde 24～28ml/L, metal salt 15g/L, whose mole ratio to the complex agent content was 1:5, ultrasonic and magntic stiring.
(2) The reaction mechanism of electroless copper coating was mainly studied with the help of XPS, which shows the reduction PdCl_2 (activator) catalyst on the surface of molybdenum powders by SnCl_2 (sensitizer) to produce pure Pd~0 clusters, which subsequently act as nucleation sites for copper depositon. The concept of XPS core-level binding energy(BE) shift due to small cluster size was utilized to predict the size of pure Pd~0 clusters deposited on the surface of molybdenum powders, which were about 3～4 nm. Combination the reaction mechanism of electroless copper coating and the morphologies of the copper coated powders at the different stages in this experiment, the diffusion-shrinkage autocatalytic model was supposed for the growth mechanism over the surface.
(3) The metallic Ag~0 clusters acted as nucleation sites for the copper deposition and the copper coated molybdenum composite powders can be acquired successfully. With the analysis of XPS, the reaction mechanism of electroless copper coating of molybdenum powders as Ag catalysis was suggested. After the sensitization step, the reducing agent(H_2PO_2~-) in the bath immediately reduced the [Ag(NH_3)_2]~+ ions adsorbed on the molybdenum to the metallic Ag~0 clusters which subsequently act as nucleation sites for copper depositon.
(4) The Mo/Cu composite powders were reducing treated for 60min at 350℃, which can improve the final densification of the compact. The Mo/Cu composite powders had good formability. The green compact of the relative density can reached up to 87%, however it needed higher forming pressure.
(5) The preparation of Mo/Cu composite materials with liquid sintering and solid sintering methods was discussed, respectively. The liquid sintering method was not ideal way to fabricate the Mo/Cu composite materials, because after liquid sintering the phenomena of copper exudation and collapse were observed. After Mo/Cu green compacts were sintered to composite materials at temperature that was lower than the melting point of copper. The conductivity, heat conductivity, heat expansion coefficient and rigid were detected. The results showed that properties composites materials were excellent due to the special structure of Mo/Cu composite powders.
引文
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